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Crown ether (CE)-based Li adsorbent microfibers (MFs) were successfully fabricated through a combined use of CE diols, electrospinning, and aerosol cross-linking. The 14- to 16-membered CEs, with varied ring subunits and cavity dimensions, have two hydroxyl groups for covalent attachments to poly(vinyl alcohol) (PVA) as the chosen matrix. The CE diols were blended with PVA and transformed into microfibers via electrospinning, a highly effective technique in minimizing CE loss during MF fabrication. Subsequent aerosol glutaraldehyde (GA) cross-linking of the electrospun CE/PVA MFs stabilized the adsorbents in water. The aerosol technique is highly effective in cross-linking the MFs at short time (5 h) with minimal volume requirement of GA solution (2.4 mL g MF). GA cross-linking alleviated CE leakage from the fibers as the CEs were securely attached with PVA through covalent CE-GA-PVA linkages. Three types of CE/PVA MFs were fabricated and characterized through Fourier transform infrared-attenuated total reflection, C cross-polarization magic angle spinning NMR, field emission scanning electron microscope, N adsorption/desorption, and universal testing machine. The MFs exhibited pseudo-second-order rate and Langmuir-type Li adsorption. At their saturated states, the MFs were able to use 90-99% CEs for 1:1 Li complexation, suggesting favorability of their microfibrous structures for CE accessibility to Li. The MFs were highly Li-selective in seawater. Neopentyl-bearing CE was most effective in blocking larger monovalents Na and K, whereas the dibenzo CE was best in discriminating divalents Mg and Ca. Experimental selectivity trends concur with the reaction enthalpies from density functional theory calculations, confirming the influence of CE structures and cavity dimensions in their "size-match" Li selectivity.

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